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1.
Reaction of the cluster salt [(η5-Cp)3Mo3S4][pts] ([1][pts], Cp=methylcyclopentadienyl; pts=p-toluenesulfonate) with CuCl yielded a new heterobimetallic cluster, [(η5-Cp)3Mo3S4Cu(Cl)][pts] ([2][pts]). X-ray crystal structure determination of [1][pts] and [2][pts] showed that the incorporation of CuCl into the Mo3S4 cluster core has only minor consequences on the Mo-Mo and Mo-S distances. The metal atoms in the cluster core of [2]+ form an almost regular tetrahedron. The [2]+ cation conforms to an idealized C3v symmetry ignoring the Cp groups since the Cu-Cl bond is almost aligned with the axis defined by the Cu-S(4) cube diagonal.  相似文献   

2.
Two closely related 1:1 salts are obtained upon electrocrystallization of BEDT-TTF (BEDT-TTF: bis(ethylenedithio)tetrathiafulvalene) in the presence of the isosteric [M(tfadt)2] dithiolene complexes (tfadt: 1-trifluoromethyl-2-cyano-1,2-dithiolato), which essentially differ by their spin state, S = 0 in [Au(tfadt)2], S = 1/2 in [Ni(tfadt)2]. In both [BEDT-TTF][M(tfadt)2] salts, the BEDT-TTF radical cations form chains with a strong lateral overlap and strong antiferromagnetic interactions while the paramagnetic anions in the nickel-containing salt [BEDT-TTF][Ni(tfadt)2] are essentially non-interacting. The structural differences between the nickel and gold complexes are analyzed and discussed.  相似文献   

3.
Pressure-tuning infrared spectra (up to ca. 40 kbar) are reported for Magnus’ Green salt, [Pt(NH3)4][PtCl4] and two of its derivatives, [Pt(ND3)4][PtCl4] and [Pt(NH3)4][PtBr4]. The spectroscopic data indicate that there is restricted rotation of the coordinated ammonia groups about the Pt-N bonds in the complexes. It is possible that this restricted rotation is due to the presence of weak hydrogen bonding to the halogens, i.e., N-H?X (X = Cl, Br) interactions.  相似文献   

4.
The reaction of [N(PPh3)2]2[Ni6(CO)12] with Cu(PPh3)xCl (x=1, 2), as well as the degradation of [N(PPh3)2]2[H2Ni12(CO)21] with PPh3, affords the new and unstable dark orange–brown [N(PPh3)2]2[Ni9(CO)16].THF salt in low yields. This salt has been characterized by a CCD X-ray diffraction determination, along with IR spectroscopy and elemental analysis. The close-packed two-layer metal core geometry of the [Ni9(CO)16]2− dianion is directly related to that of the bimetallic [Ni6Rh3(CO)17]3− trianion and may be envisioned to be formally derived from the hcp three-layer geometry of [Ni12(CO)21]4− by the substitution of one of the two outer [Ni3(CO)3(μ−CO)3]2− layers with a face-bridging carbonyl group.  相似文献   

5.
6.
The trinuclear arene-ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+, containing a μ3-oxo cap and three arene ligands that span a hydrophobic pocket above the metal skeleton, has been crystallised as tetrafluoroborate salt in the presence of various guest molecules. The host-guest complexes have been characterised by single-crystal X-ray structure analysis. With chloroform as the guest molecule, a CHCl3 molecule sits perfectly in the hydrophobic pocket, the hydrogen atom being encapsulated inside the cavity. When dioxane is added during the crystallisation process, the cluster forms infinite chains which are connected by a complex network of hydrogen bonds involving the μ3-oxo ligand, water and dioxane molecules. Interestingly, in the presence of phenol, a water molecule is hydrogen-bonded between the μ3-oxo ligand and the phenol molecule, forming a one-dimensional μ3-O ? H2O ? HO hydrogen-bonded chain. Finally, with benzoic acid, a head-to-tail host-guest chain is obtained, the phenyl ring being incorporated in the hydrophobic pocket, while the acid group is hydrogen-bonded to the μ3-oxo ligand.  相似文献   

7.
The reaction of ReH92− with Mo(diglyme)(CO)3 leads to the formation of the mixed metal cluster trianion, ReMo3H4(CO)123−. This species has been characterized analytically, spectroscopically and through X-ray diffraction analysis. A pseudo-tetrahedral arrangement of M(CO)3 fragments is adopted, such that each set of three carbonyl ligands eclipses the adjacent three tetrahedral edges, an apparent result of the location of the hydride ligands on the tetrahedral faces. Variable temperature NMR studies revealed a fluctional process for some of the carbonyl ligands, but not for the hydrides. Crystal data for [Me4N]3[ReMo3H4(CO)12]·THF; space group P21/n, a = 12.157(2), B = 21.480(4), C = 15.964(3) Å, β = 98.26(1)°, Z = 4, R = 0.067 and Rw = 0.076.  相似文献   

8.
A new polyoxomolybdenum compound [Mo4O12(2,2′-bpy)3]n (1) (2,2′-bpy = 2,2′-bipyridine) has been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TG analysis, and single crystal X-ray diffraction. The solid state structure is a 1D chain with a repeat unit of three corner-sharing {MoO4N2} octahedra and one {MoO4} tetrahedron.  相似文献   

9.
The hydrothermal reaction of a solution of Ni(CH3CO2)2 · 4H2O, MoO3, tetra-4-pyridylpyrazine, H2O3PCH3, and HF at 200 °C for 96 h yields orange crystals of [Ni(tpyrpyz)2]2[Mo4O12F2][Mo6O17] · 2H2O (1 · 2H2O). The structure consists of discrete {Ni(tpyrpyz)2}2+ cations and {Mo6O19}2− and {Mo4O12F2}2− anionic clusters. The hexamolybdate is the well-documented octahedron of octahedra, that is, six {MoO6} octahedra in a compact edge-sharing arrangement. The novel oxyfluoride cluster {Mo4O12F2}2− features two {MoO4F2} octahedra, sharing the edge defined by the fluoride ligands; the octahedral Mo sites corner-share to two {MoO4} tetrahedra in the μ2-O, O bridging mode.  相似文献   

10.
Mono- and bis-substituted phosphite complexes [Ru3(CO)12−x Lx] (L = tris(2,4-di-tert-butylphenyl) phosphite; x = 1, 2) were synthesized by simple substitution reactions, and were characterized by spectroscopic methods. The monosubstituted ruthenium complex disproportionates in acetone producing a mononuclear ruthenium complex as one of the decomposition products. Single crystal X-ray diffraction analysis established the molecular structure of this new compound.  相似文献   

11.
The reactions of the Keplerate super cluster [Mo132O372(CH3CO2)30(H2O)72]42− with a Cu(II) source and an organonitrogen donor in methanol/DMF solutions yielded a series of bimetallic organic-inorganic oxide hybrid materials, including the molecular species [Cu(phen)2MoO4] (1) and [{Cu(terpy)}2(MoO4)2] (2) and a series of materials constructed from the tetranuclear building block {Mo4O10(OMe)6}2−: the molecular [{Cu2(phen)2(O2CCH3)2 (MeOH)}Mo4O10(OMe)6] (3), [{Cu(terpy)(O2CCH3)}2Mo4O10(OMe)6] (4) and [{Cu(terpy)Cl}2Mo4O10(OMe)6] (5), the one-dimensional phases [{Cu(bpy)(HOMe)2}Mo4O10(OMe)6] (6), [{Cu(bpy)(DMF)2}Mo4O10(OMe)6] (7), [{Cu(bpa)(DMF)2}Mo4O10(OMe)6] (8), [{Cu(phen)(DMF)2}Mo4O10(OMe)6] (9) and [{CuCl(dpa)}2Mo4O10(OMe)6] (10), and the two-dimensional material [{Cu2(DMF)2(pdpa)}{Mo4O10(OMe)6}2] (11). When methanol is replaced by the tridentate alkoxide tris-methoxypropane (trisp), the {Mo2O4(trisp)2}2− cluster building block is observed for [Cu(phen)Mo2O4(trisp)2] (12), [Cu(bpa)(DMF)Mo2O4(trisp)2] (13) and [{Cu(bpy)(NO3)}2Mo2O4(trisp)2] (14).  相似文献   

12.
A room-temperature reaction between [Re6S8(OH)6]4− and acetic acid in an aqueous solution resulted in the substitution of all terminal hydroxo groups by acetate ligands, affording a new hexanuclear anionic rhenium cluster complex [Re6S8(CH3COO)6]4−. The complex was isolated as a potassium salt with the composition of K4[Re6S8(CH3COO)6]·8H2O (1) and characterized by X-ray single-crystal diffraction and elemental analyses, IR, 1H NMR, UV-Vis, and luminescence spectroscopies.  相似文献   

13.
Analogy with the isolable oxo cluster [Fe3(CO)93-O)]2−, which is structurally interesting and synthetically useful, prompted the present attempt to synthesize its ruthenium analog. Although the high reactivity of [Ru3(CO)93-O)]2− (I) prevented its isolation, the reaction of this species with [M(CO)3(NCCH3)]+, where M = Mn or Re, yields [PPN][MRu3(CO)1223-NC(μ-O)CH3]. The high nucleophilicity of the oxo ligand in [Ru3(CO)93-O)]2− (I) appears to be responsible for the conversion of acetonitrile to an acetamidediato ligand and for the instability of I. The crystal structure of [PPN][MnRu3(CO)1223-NC(μ-O)CH3)]] reveals a hinged butterfly array of metal atoms in which the acetamidediato ligand bridges the two wings with μ3-N bonding to an Mn and two Ru atoms, and μ-O bonding to an Ru atom.  相似文献   

14.
A novel Ni(II)-nitronyl nitroxide-substituted thiazole complex, Ni(NIT2-thz)3(ClO4)2 (NIT2-thz = 2-(2′-thiazole)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group P21c. The metal coordination sphere is fully occupied by three chelating nitroxide ligands, showing a distorted octahedral geometry. The complex molecules were connected as 1-D chain structure by the intermolecular interaction. Magnetic studies show that antiferromagnetic couplings occurred between the nickel(II) ion and the organic radicals, and ferromagnetic between the adjacent molecules.  相似文献   

15.
Reactions of a single-cubane cluster [{Rh(cod)}2{MoCl(dtc)}23-S)4] (cod = 1,5-cyclooctadiene, dtc = diethyldithiocarbamate) with 1 equiv. of L (L = pyrazine, 4,4′-bipyridyl, trans-1,2-bis(4-pyridyl)ethylene) in the presence of 2 equiv. of AgBF4 in CH2Cl2 gave doubly bridged double-cubane clusters [({Rh(cod)}2{Mo(dtc)}23-S)4)2(μ-L)2][BF4]4, whose structures were determined by the single-crystal X-ray analysis.  相似文献   

16.
The mineral helvite, (Mn4S)(BeSiO4)3, contains discrete tetrahedral Mn4S+6 clusters in which the S?2 is tetrahedrally coordinated and each Mn(II) is in a distorted tetrahedron of one S?2 and three oxygens; the cluster is situated within an encompassing lattice of SiO4?4 and BeO4?6 tetrahedra. Mn4S+6 centers provide an interesting model for comparison to the polynuclear manganese center that is associated with photosynthetic water oxidation. Magnetic susceptibility data between 77 and 298 K have been measured for a natural helvite sample containing principally Mn4S+6 centers but with significant contamination from Mn3FeS+6 and Mn3CaS+6. The data exhibited Curie-Weiss behavior with μeff = 5.969 B.M. and θ = 178.3 K. An analysis of the magnetic susceptibility, based on Van Vleck's formalism, demonstrated the presence of antiferromagnetic coupling, with a coupling constant J = ?5.83 cm?1. Mössbauer spectra of Mn3FeS centers in helvite and of Fe4S centers in the related mineral danalite have also been recorded. Isomer shifts show little temperature dependence and lie in the range 1.23–1.43 mmsec.. This range is typical of tetrahedrally coordinated Fe(II) in several ionic crystals but is significantly above that of Fe(II) in ferredoxins and below that in the [quinone-Fe(II)-quinone] complex of the photosynthetic bacterium,Rhodopseudomonas sphaeroides. Quadrupole splittings are highly temperature dependent, ranging from 2.4 mmsec at 4.2 K to less than 0.5 mmsec at 248 K.  相似文献   

17.
The hydrothermal reaction of MoO3, [Cu(CH3CO2)2] · H2O, 2,2:6,2″-terpyridine (terpy), H2O3AsC6H5, H2O and H2SO4 yields aqua colored crystals of [{Cu(terpy)}2Mo12O34(O3AsC6H5)4] · 2.25H2O (1 · 2.25H2O). The two-dimensional structure of 1 is constructed from {Mo12O34(O3AsC6H5)4}4− clusters linked through {Cu(terpy)}2+ subunits. Each Cu(II) site exhibits {CuN3O2} coordination geometry and links two adjacent clusters. In turn, each cluster is associated with four Cu(II) sites through {MoO · Cu} interactions.  相似文献   

18.
The in-situ formed hydrazone Schiff base ligand (E)-N′-(2-oxy-3-methoxybenzylidene)benzohydrazide (L2−) reacts with copper(II) acetate to a tetranuclear open cubane [Cu(L)]4 complex which crystallizes as two symmetry-independent (Z′ = 2) S4-symmetrical molecules in different twofold special positions with a homodromic water tetramer. The two independent (A and B) open- or pseudo-cubanes with Cu4O4 cores of 4 + 2 class (Ruiz classification) each have three different magnetic exchange pathways leading to an overall antiferromagnetic coupling with J1B = J2B = −17.2 cm−1, J1A = −36.7 cm−1, J2A = −159 cm−1, J3A = J3B = 33.5 cm−1, g = 2.40 and ρ = 0.0687. The magnetic properties have been analysed using the H = −Σi,jJij(SiSj) spin Hamiltonian.  相似文献   

19.
We previously designed and synthesized a series of histamine analogues with an imidazolylcyclopropane scaffold and identified potent non-selective antagonists for histamine H3 and H4 receptor subtypes. In this study, to develop H4 selective ligands, we newly designed and synthesized cyclopropane-based derivatives having an indole, benzimidazole, or piperazine structure, which are components of representative H4 selective antagonists such as JNJ7777120 and JNJ10191584. Among the synthesized derivatives, imidazolylcyclopropanes 12 and 13 conjugated with a benzimidazole showed binding affinity to the H3 and H4 receptors comparable to that of a well-known non-selective H3/H4 antagonist, thioperamide. These results suggest that the binding modes of the cyclopropane-based H3/H4 ligands in the H4 receptor can be different from those of the indole/benzimidazole-piperazine derivatives.  相似文献   

20.
The hydrothermal reaction of NiCl2·6H2O, MoO3, 3,4′-bipyridine (3,4′-bpy) and H2O in the mole ratio 1.0:1.0:2.1:1500 yields [Ni(3,4′-bpy)2MoO4]·3H2O (1·3H2O) in 80% yield. The structure of 1·3H2O consists of a three-dimensional coordination polymer {Ni(3,4′-bpy)2}n2n+ with entrained {MoO4}2− tetrahedra and with water molecules of crystallization occupying channels within the bimetallic oxide-ligand framework. Crystal data: C20H16N4O4NiMo·3H2O (1·3H2O), tetragonal P41212, a=13.1866(5) Å, c=29.458(2) Å, V=5122.3(4) Å3, Z=8, Dcalc=1.532 g cm−3.  相似文献   

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